Methylcyclopentyl phosphate and phosphonate esters



United States Patent 3,514,505 METHYLCYCLOPENTYL PHOSPHATE ANDPHOSPHONATE ESTERS Gerald H. Peterson, 11972% Idaho,

West Los Angeles, Calif. 90025 5 No Drawing. Filed Aug. 28, 1967, Ser.No. 663,541 Int. Cl. C07f 9/08, 9/38; C09k 3/00 US. Cl. 260-958 13Claims ABSTRACT OF THE DISCLOSURE This invention relates to chemicalcompounds which are phosphate esters and phosphonate esters having threeorganic radicals at least one of which is the l-methylcyclopentyl or the2-methylcyclopentyl and the other organic radicals of which are thel-methylcyclopentyl radical, the 2-methylcyclopentyl radical, the phenylradical, or the tolyl radical.

These chemical compounds are useful for thermally stable fire resistanthydraulic fluids, especially for aircraft, either alone or admixed withother additives.

Tri-l-methlycyclopentyl phosphate Di-l-methylcyclopentyl phenylphosphate Mono-l-methylcyclopentyl di-phenyl phosphateDi-l-methylcyclopentyl tolyl phosphate Mono-l-methylcyclopentyl di-tolylphosphate Mono-l-methylcyclopentyl tolyl phenyl phosphate (2) Phosphateesters having the l-methylcyclopentyl radical:

Di-l-methylcyclopentyl l-methylcyclopentane phosphonateDi-l-methylcyclopentyl benzene phosphonate Di-phenyll-methylcyclopentane phosphonate Di-l-methylcyclopentyl toluenephosphonate Di-tolyl l-methylcyclopentane phosphonateMono-l-methylcyclopentyl tolyl benzene phosphonateMono-l-methylcyclopentyl phenyl toluene phosphonate (3) Phosphate estershaving the 2-methylcyclopentyl 5 radical:

Tri-Z-methylcyclopentyl phosphate Di-Z-methylcyclopentyl phenylphosphate Mono-2-methylcyclopentyl di-phenyl phosphateDi-Z-methylcyclopentyl tolyl phosphate Mono-2-methylcyclopentyl di-tolylphosphate Mono-Z-methylcyclopentyl tolyl phenyl phosphate (4)Phosphonate esters having the 2-mthylcyclopentyl radical: 6

Di-Z-methylcyclopentyl 2-methylcyclopentane phosphonateDi-Z-methylcyclopentyl benzene phosphonate Di-phenyl2-methylcyclopentane phosphonate Di-Z-methylcyclopentyl toluenephosphonate Di-tolyl Z-methylcyclopentane phosphonate 3,514,505 PatentedMay 26, 1970 Mono-2-methylcyclopentyl tolyl benzene phosphonateMono-2-methylcyclopentyl phenyl toluene phosphonate Thel-methylcyclopentyl radical is shown as follows: on, H HC The2-methylcyclopentyl radical is shown as follows:

l. in

Each of these new foregoing chemical compounds can be made by the samemethods used for making the corresponding phosphates and phosphonateswhere the butyl radical is used instead of the l-methylcyclopentylradical or the Z-methylcyclopentyl radical. The methods of making thecorresponding phosphates and phosphonates with butyl radical are knownto those skilled in the art, and with the disclosure herein thoseskilled in the art to which my invention appertains will be able to makeand use the new chemical compounds of my invention.

The preparation of the known phosphate esters and phosphonate estershaving the butyl radical instead of the l-methylcyclopentyl radical or2-methylcyclopentyl radical of my invention is disclosed in the booksentitled Introduction to Hydraulic Fluids by Roger E. Hatton, publishedby Reinhold Publishing Corporation, Organo- Phosphorous Compounds by G.M. Kosolopotf, published by John Wiley and Sons, Synthetic Lubricantsedited by Reigh C. Gunderson and Andrew W. Hart, published by ReinholdPublishing Corporation, New York, and numerous other publications andissued patents. The particular relevant disclosure in the book entitledIntroduction to Hydraulic Fluids appears on pp. through 195, and theparticular relevant disclosure in the book entitled Synthetic Lubricantsappears on pp. 103 through 150.

Even though those skilled in the art will be able to prepare and use thenew chemical compounds of my inventions, there is given below examplesof these compounds and their preparation.

EXAMPLE 1 Tri-l-methylcyclopentyl phosphate 3.5 mols ofl-methylcyclopentyl alcohol are added dropwise with stirring to 1 mol ofphosphorus oxychloride (POCl at 2535 C. The temperature is slowlybrought up to about 65 C. and the pressure is slowly reduced to 50mm./Hg with stirring to remove hydrogen chloride. The mixture is thendistilled and tri-l-methylcyclopentyl phosphate is collected.

EXAMPE 2 Tri-l-methylcyclopentyl phosphate To 5 mols ofl-methylcyclopentanol, 3 mols of freshly cut metallic sodium are addedin small cubes about /4 with stirring and maintaining the temperaturebetween 25 and 40 C. When reaction is complete as evidenced by cessationof bubbling, 1 mol of phosphorus oxychloride is added dropwise withstirring while maintaining the temperature at about 25-50" C. Thereaction mixture is filtered to remove the precipitated sodium chlorideand the filtrate is distilled and tri-l-methylcyclopentyl phosphate iscollected.

3 EXAMPLE 3 Di-l-methylcyclopentyl phenyl phosphate 2 mols ofl-methylcyclopentanol are added dropwise with stirring to 1 mol of POClat 25-35 C. The temperature is slowly brought up to about 65 C. and thepressure slowly reduced to 50 mm./ Hg to remove hydrogen chloride.Without further purification this mixture is added dropwise at -5 C. toa saturated solution of 1 mol of phenol in 1 mol of sodium hydroxidewith good stirring. The mixture is allowed to rise in temperature to 25C. with continued stirring. The resulting mixture is washed, dried anddistilled to separate out the desired water insolubledi-l-methylcyclopentyl phenyl phosphate.

EXAMPLE 4 D't-l-methylcyclopentyl tolyl phosphate 2 mols ofl-methylcyclopentanol are added dropwise with stirring to 1 mol of POClat 25-35 C. The temperature is slowly brought up to about 65 C. and thepressure slowly reduced to 50 mm./Hg to remove hydrogen chloride.Without further purification this mixture is added dropwise at 05 C. toa saturated solution of 1 mol of meta-cresol in 1 mol of sodiumhydroxide with good stirring. The mixture is allowed to rise intemperature to 25 C. with continued stirring. The resulting mixture iswashed, dried and distilled to separate out the desired water insolubledi-l-methylcyclopentyl meta-tolyl phosphate.

EXAMPLE 5 Mono-l-methylcyclopentyl di-phenyl phosphate 1 mol ofl-methylcyclopentanol is added dropwise with stirring to 1 mol of POClat 2535 C. The temperature is slowly brought up to about 65 C. and thepressure slowly reduced to 50 mm./Hg to remove hydrogen chloride.Without further purification this mixture is added dropwise at 0-5 C. toa saturated solution of 2 mols of phenol in 2 mols of NaOH with goodstirring. The mixture is allowed to rise in temperature to 25 C. withcontinued stirring. The resulting mixture is washed, dried and distilledto separate out the desired water insoluble mono-l-methylcyclopentyldi-phenyl phosphate.

EXAMPLE 6 Mono-1-methylcyclopentyl para-tolyl phosphate 1 mol ofl-methylcyclopentanol is added dropwise with stirring to 1 mol of POClat 2535 C. The temperature is slowly brought up to about 65 C. and thepressure slowly reduced to 50 mm./Hg to remove hydrogen chloride.Without further purification this mixture is added dropwise at 0-5 C. toa saturated solution of 2 mols of para-cresol in 2 mols of NaOH withgood stirring. The mixture is allowed to rise in temperature to 25 C.with continued stirring. The resulting mixture is washed, dried anddistilled to separate out the desired water insolublemono-l-methylcyclopentyl para-tolyl phosphate.

EXAMPLE 7 Mono-l-methylcyclopentyl phenyl tolyl phosphate 1 mol ofl-methylcyclopentanol is added dropwise with stirring to 1 mol of POClat 25-35" C. The temperature is slowly brought up to about 65 C. and thepressure slowly reduced to 50 mm./Hg to remove hydrogen chloride.Without further purification this mixture is added dropwise at 0-5 C. toa saturated solution of 1 mol of phenol in 1 mol of sodium hydroxidewith good stirring. The mixture is allowed to rise in temperature to 25C. with continued stirring. The mixture is filtered and the filtrate isadded dropwise, without further purification, at 0-5 C. to a saturatedsolution of 1 mol of meta-cresol in 1 mol of NaOH with good stirring.The mixture is allowed to rise in temperature with continued stirring.The resulting mixture is washed, dried and dis- 4 tilled to separate outthe desired water insoluble mono-lmethylcyclopentyl phenyl meta-tolylphosphate.

EXAMPLE 8 Di-l-methylcyclopentyl l-methylcyclopentane phosphate 3 molsof l-methylcyclopentanol are added dropwise with stirring to 1 mol of1-methylcyclopentane phosphorus oxydichloride at 25-35 C. Thetemperature is slowly brought up to about 65 C. and the pressure isslowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride.The mixture is then distilled and di-lmethylcyclopentyll-methylcyclopentane phosphate is collected.

EXAMPLE 9 Di-phenyl-l-methylcyclopentane phosphonate 3 mols of phenolare added dropwise with stirring to 1 mol of l-methylcyclopentanephosphorus oxydichloride at 25-35 C. The temperature is slowly broughtup to about 65 C. and the pressure is slowly reduced to 50 mm./Hg withstirring to remove hydrogen chloride. The mixture is then distilled anddi-phenyl l-methylcyclopentane phosphonate is collected.

EXAMPLE 10 Di-meta-tolyl l-methylcyclopentane phosphonate 3 mols ofmeta-cresol are added dropwise with stirring to 1 mol ofl-methylcyclopentane phosphorus oxydichloride at 2535 C. The temperatureis slowly brought up to about 65 C. and the pressure is slowly reducedto 50 mm./Hg with stirring to remove hydrogen chloride. The mixture isthen distilled and di-meta-tolyl l-methylcyclopentane phosphonate iscollected.

EXAMPLE 11 l-methylcyclopentyl meta-tolyl l-methylcyclopentanephosphonate 1 mol of l-methylcyclopentanol is added dropwise withstirring to 1 mol of l-methylcyclopentane phosphorus oxydichloride at2535 C. The temperature is slowly brought up to about 65 C. and thepressure is slowly reduced to 50 mm./ Hg with stirring to removehydrogen chloride. Without further purification this mixture is addeddropwise at 0-5 C. to a saturated solution of 1 mol of meta-cresol in 1mol of sodium hydroxide with good stirring. The mixture is allowed torise in temperature to 25 C. with continued stirring. The resultingmixture is washed, dried and distilled to separate out the desired waterinsoluble l-methylcyclopentyl meta-tolyl lmethylcyclopentanephosphonate.

EXAMPLE 12 l-methylcyclopentyl phenyl l-methylcyclopentane phosphonate 1mol of l-methyl cyclopentanol is added dropwise with tirring to 1 mol ofl-methylcyclopentane phosphorus oxydichloride at 25-35 C. Thetemperature is slowly brought up to about 65 C. and the pressure isslowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride.Without further purification this mixture is added dropwise at 0-5" C.to a saturated solution of 1 mol of phenol in 1 mol of sodium hydroxidewith good stirring. The mixture is allowed to rise in temperature to 25C. with continued stirring. The resulting mixture is washed, dried anddistilled to separate out the desired water insolublel-methylcyclopentyl phenyl l-methylcy clopentane phosphonate.

EXAMPLE 13 Di-l-methylcyclopentyl benzene phosphonate 3 mols ofl-methylcyclopentanol are added dropwise with stirring to 1 mol ofbenzene phenyl phosphorus oxydichloride at 25-35 C. The temperature isslowly brought up to about 65 C. and the pressure is slowly reduced to50 mm./Hg with stirring to remove hydrogen chloride. The mixture is thendistilled anddi-l-methylcyclopentyl benzene phosphonate is collected.

EXAMPLE 14 Di-l-methylcyclopentyl toluene phosphonate 3 mols ofl-methylcyclopentanol are added dropwise with stirring to 1 mol ofmeta-toluene phosphorus oxydichloride at 2535 C. The temperature isslowly brought up to about 65 C. and the pressure is slowly reduced to50 mm./Hg with stirring to remove hydrogen chloride. The mixture is thendistilled and di-l-methylcyclopentyl toluene phosphonate is collected.

EXAMPLE 15 l-methylcyclopentyl phenyl benzene phosphonate 1 mol ofl-methylcyclopentanol i added dropwise with stirring to 1 mol of benzenephosphorus oxydichloride at 2535 C. The temperature is slowly brought upto about 65 C. and the pressure is slowly reduced to 50 mm./Hg withstirring to remove hydrogen chloride. Without further purification thismixture is added dropwise at -5 C. to a saturated solution of 1 mol ofphenol in one mol of sodium hydroxide with good stirring. The mixture isallowed to rise in temperature to 25 C. with continued stirring. Themixture is Washed, dried, and distilled and l-methylcyclopentyl phenylbenzene phosphonate is collected.

EXAMPLE 16 l-methylcyclopentyl meta-tolyl benzene phosphonate 1 mol ofl-methylcyclopentanol is added dropwise with stirring to 1 mol ofbenzene phosphorus oxydichloride at 25-35 C. The temperature is slowlybrought up to about 65 C. and the pressure is slowly reduced to 50mm./Hg with stirring to remove hydrogen chloride. Without furtherpurification this mixture is added droplwise at 0-5 C. to a saturatedsolution of 1 mol of metacresol in 1 mol of sodium hydroxide with goodstirring. The mixture is allowed to rise in temperature to 25 C. withcontinued stirring. The mixture is washed, dried and distilled andl-methylcyclopentyl meta-tolyl benzene phosphonate is collected.

EXAMPLE 17 l-methylcyclopentyl tolyl toluene phosphonate 1 mol ofl-methylcyclopcntanol is added dropwise with stirring to 1 mol ofmeta-toluene phosphorus oxydichloride at 25-35 C. The temperature isslowly brought up to about 65 C. and the pressure is slowly reduced to50 mm./Hg with stirring to remove hydrogen chloride. Without furtherpurification this mixture is added dropwise at 05 C. to a saturatedsolution of 1 mol of metacresol in 1 mol of sodium hydroxide with goodstirring. This mixture is allowed to rise in temperature to 25 C. withcontinued stirring. The mixture is washed, dried and distilled andl-methylcyclopentyl tolyl toluene phosphomate is collected.

EXAMPLE 18 l-methylcyclopentyl phenyl toluene phosphonate 1 mol ofl-methylcyclopentanol is added dropwise with stirring to 1 mol ofmeta-toluene phosphorus oxydichloride at 2535 C. The temperature isslowly brought up to about 65 C. and the pressure is slowly reduced to50 mm./Hg with stirring to remove hydrogen chloride. Without furtherpurification this mixture is added dropwise at 05 C. to a saturatedsolution of 1 mol of phenol in 1 mol of sodium hydroxide with goodstirring. This mixture is allowed to rise in temperature to 25 C. withcontinued stirring. The mixture is washed, dried ,and distilled and1-methylcyclopentyl phenyl toluene phosphonate is collected.

EXAMPLE 19 Tolyl phenyl l-methylcyclopentane phosphonate 1 mol ofmeta-cresol is added dropwise with stirring to 1 mol ofl-methylcyclopentane phosphorus oxydichlorlde at 25-35 C. Thetemperature is slowly brought up to about 65 C. and the pressure isslowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride.Without further purification this mixture is added dropwise at 0-5 C. toa saturated solution of 1 mil of phenol in 1 mol sodium hydroxide withgood stirring. This mixture is allowed to rise in temperature to 25 C.with continued stirring. The mixture is Washed, dried and distilled andtolyl phenyl l-methylcyclopentane phosphonate is collected.

The foregoing examples illustrate the phosphonate and phosphonate estersof my invention with the l-methylcyclopentyl radical. It will beunderstood of course in 'each of the foregoing examples theZ-methylcyclopentyl properties, and are readily admixed with manyadditives.

I claim:

1. The phosphate and phosphonate esters represented by the formula (R RRQO O PO in which x may be one or zero, R is l-methylcyclopentyl orZ-methylcyclopentyl, and R and R are l-methylcyclopentyl,Z-methylcyclopentyl, phenyl, or tolyl.

2. The chemical compound as defined in claim 1 which istri-methylcyclopentyl phosphate.

3. The chemical compound as defined in claim 1 which isdi-methylcyclopentyl methylcyclopentane phosphonate.

4. The chemical compound as defined in claim 1 which isdi-methylcyclopentyl phenyl phosphate.

5. The chemical compound as defined in claim 1 which isdi-methylcyclopentyl benzene phosphonate.

6. The chemical compound as defined in claim 1 whichdi-methylcyclopentyl tolyl phosphonate.

7. The chemical compound as defined in claim 1 which ismono-methylcyclopentyl di-phenyl phosphate.

8. The chemical compound as defined in claim 1 which ismono-methylcyclopentyl phenyl benzene phosphonate.

9. The chemical compound as defined in claim 1 which ismono-metbylcyclopentyl di-tolyl phosphate.

10. The chemical compound as defined in claim 1 which ismono-methylcyclopentyl tolyl toluene phosphonate.

11. The chemical compound as defined in claim 1 which ismono-methylcyclopentyl tolyl phenyl phosphate.

12. The chemical compound as defined in claim 1 which ismono-methylcyclopentyl tolyl benzene phosphonate.

, 13. The chemical compound as defined in claim 1 which ismono-methylcyclopentyl phenyl toluene phosphonate.

References Cited UNITED STATES PATENTS 1,959,228 5/1934 Blagden et al.260-958 XR 2,682,522 6/1954 Coover et al. 260958 XR CHARLES B. PARKER,Primary Examiner A. H. SUTTO, Assistant Examiner US. Cl. X.R. 260973,974; 25278

